CA1037338A

CA1037338A - Liquid cleaning composition

Info

Publication number: CA1037338A
Application number: CA222,382A
Authority: CA
Inventors: William J. Lautenberger; Helmut H. Froehlich
Original assignee: Milliken Research Corp
Current assignee: Milliken Research Corp
Priority date: 1974-03-18
Filing date: 1975-03-18
Publication date: 1978-08-29
Also published as: DE2511854B2; GB1467583A; FR2264868A1; US3910848A; DE2511854A1; FR2264868B1; DE2511854C3; JPS50127905A; JPS5427003B2

Abstract

LIQUID CLEANING COMPOSITION

ABSTRACT OF THE DISCLOSURE

A liquid cleaning dispersion comprising a halo-genated solvent and urea-formaldehyde polymer particles as the major components, also with small amounts of an anti-static agent and an antisettling agent and, optionally, chlorofluorinated propellant for aerosol applications;
useful for cleaning textiles.

Description

BACKGROUND OF THE INVENTION
~ . _ This invention concerns ah all-purpose cleaning composition~ in the form of a liquid dispersion, that is especially useful on carpets~and upholstery.
Many known spot-removing compositions employ a solvent/adsorbent substrate com~ination. The solvent mobilizes the soil and the adsorbent substrate attracts the soil and s~lvent to itself for removal from the fabric by, say, brushing or ~acuuming, Detergents and/or sur-factants are sometimes employed in such cleaning composi-tions. The surfactants are usually anionic or nonionic in character. Examples of anionic surfactants include salts of fatty acids, alcohol sulfates and sulfonates, polyoxy-alkylene alkyl carboxylates and polyoxyalkylene alcohol phosphates. Nonionic surfactants include polyethoxylated alcohols, amines, alkyl phenols~ fatty acids and amides.
When textile products, particularly carpets and upholstery, are cleaned with such prior art compositions the very fine particles of adsorbent substrate tend to adhere to the textile fibers~ This is particularly - noticeable when the fibers and the particulates are non-conductive. The phenomenon is believed due to static ';'' ~ ',: ''` ': ' '' ': ' ' ~ ' ` ' `

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attraction. The compositions of the instant invention solve the problem by mncluding in the cleaner composition a cationic antistatic substance which promotes the removal of fine particulates by brushing or vacuuming the textile material. There is nothing in the art to suggest the particular combination of cleaning composition elements that are disclosed herein or to suggest employing such elements in the amounts and ratios taught herein.
SUMMARY OF THE INVENTION
This invention concerns a liquid cleaning 60m- .
position compris~ng : ?
i) 5 to 30 parts of urea-formaldehyde polymer particles having a particle size of from lO
to 105 microns and an oil value of at least 9 0, ii) 70 to 95 parts of halogenated solvent boiling at from 45to 120C., the total of i) and ii) being 100 parts, and ;~ -iii) 0.1 to 3.0 parts of finely divided silica antisettling agent, ;;~ `
iv) 0.1 to 2.0 parts of cationic antistatic agent, and v) up to 125 parts of aerosol propellant selected from at least one of trichloro-fluoromethane, di~hlorodifluoromethane, 1,2-l~'dichlorotetrafluoroethane, propane, isobutane and butane.
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~i~. . :

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A preferred cleaning composit~ons of this invention comprises i) 10 to 23 parts of urea-formaldehyde polymer particles, ii) 77 to 90 parts of halogenated solvent, iii) 0.5 to 1 part of finely divided silica, iv) 0.3 to 1 part of cationic antistatic agent, and v) up to 50 parts of aerosol propellant.
Minor amounts of additional solvents, as welll as odorants and other additives can also be included int the cleaning compositions of this inventi~n, as will be obvioas to those skilled in the art.
The cleaning compositions of the invention can be dispensed as aerosols from pressurized cans, The pro-portion of cleaner and pressurizer can best be determined ~y experiment, but will generally be approximately a 50% -~
50~ mixture. The pressurizing agents are best used as mixtures to obtain a favorable balance of properties, ~;
In use, the novel textile-cleaning compositions are applied to a soiled area of a carpet or other textile by spraying or sprinkling, or from a cloth or sponge.
applicator, and rubbed or brushed into the substrate.
After drying, which can take only seconds or a few minutes, depending on the amount applied and on atmospheric con-ditions, the residual particles can be vacuumed away or brushed into a dustpan. The soil, having been loosened by the solvent, s adsorbed on the urea-formaldehyde polymer parti¢les and is removed therewith.

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` DETAILS`` OF` TH~`'I~7EN~I~)N
~_, .
All of the individual ingredients of the composi-tions of this invention are available commercially and are made by well-known methods. The cleaning compositions are peepared by thorough mixing of the ingredients in any order.
For example, the solvent can be charged to a vessel and the antistatic and antisettling agents can be added followed by the addition of urea-formaldehyde polymer particulate material. The compositions can be packaged for use at a later date without diminution of their effectiveness.
Settling may occur on standing, but stirring or shaking be-fore use quickly restores the homogeneity of the mixture.
Urea-formaldehyde polymer particles; of satis~
factory porosity are made by reacting urea and formaldehyde `;
in an aqueous mixture at a mole ratio of about 0.9 mole urea to 1 mole of formaldehydeO Urea can be introduced ~-~:: `
as a 2~% aqueous solution and formaldehyde as a 37~ aqueous solution.
The urea solution can be made up in a reactor and the pH of the solution adjusted to 5.6-5.8 by adding sulfuric acid. The formaldehyde is best added at once, resulting ~n a lowering of pH to about 3.9. Sulfuric acid is immediately addad as catalyst~ to bring the pH
to 1.6 2Ø Polymerization starts at once, with evolution "
of heat. The charge is then heated at 55 to 60C. for two hours, and the pH is ad~usted to 7 0 to 7.5 by adding caustic soda solution. The solid particles can be removed by filtration, washed with water and dried at ~ `
about 70C After grading to eliminate particles larger and smaller than desired~ the particles are ready to use.

In order to ~unction satisfactoril~ the polymer particles must have a particle size between 10 and 105 microns. If too small, the particles will be difficult to remove from the textile fibers. I~ too large tbey will not have the desired cleaning capacity.
The oil value of the particles a function of their porosity, must be at least 90. Oil value can be determined according to Method D281 of the American Socaety for Testing Materials. In this procedure, raw linseed oil is gradually added to a weighed amount of dry, particulate material until there is obtained a stiff, putty-like paste that does not come apart easily.
Oil value for cleaning particles is calculated as ~ollows, with typical values for the specific gravity being around 1.4 g/cc:
. Grams of Oi~
01l value = G~elb~b~~lr~Rer~Cr~EaC x Sp. Gr.of particulate material x 100 The halogen-containing solvents that are useful herein are those that readily dissolve oily and greasy materials and that have satisfactory volatility. They are not so volatile as to evaporate before exerting their solvent property on the soil, but should volatilize in no ~ -more than a few minutes so that theycldonn~trp~eve~t removal of the dried soil-particulate com~ination. These properties are provided by solvents having boiling points from about 45 to 120C. Preferred solvents are ~ethyl chloroform, perchloroethylene, trichlorethylene and 1,1,2-trichloro-1,2,2~trifluoroethane. Solvent freezing ~;
points must, of course, be low enough so that the solvent doesnnot freeze at use temperatures. The most preferred solvent is l,l,1-trichloroethane, commonly called methyl chloroform.
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Contemplated chlorinated hydrocarbons are subject to decomposition upon con1act with metal surfaces. -- ?
It is therefore customary to add to these solvents small amounts of stabilizing agents. Effective stabllizers that can be used with the solvents described herein include l,4-dioxane, secondary butylene alcohol, and l,2-butylene oxide~
Cationic antistatic agents have a benefical effect on particulate recovery in the compositions of the invention. Nonionic surfactants such as trialkyl-phosphates and ethoxylated alcohols have little or no effect. Likewise, anionic surfactants such as the amine salts of alcohol phosphates and alcohol sulfates do not improve particulate recovery performance.
The preferred cationic antistatic agents that ~
are useful in the cleaning composi~ions of this i~vention - , are those that incorporate at least one Cl2 to C

aliphatic group in a quaternary salt configuration. The ~-aliphatic group can be a hydrocarbyl group or can include a linking oxygen or nitrogen atom in the chain.
The most preferred agent is stearyltrimethylammonium chloride, Good resul~s are obtained with similar com-. . ~ . ~.
pounds derived from ClO to C24 aliphatic straight chainamines.
Another series of effec~ive~ antistatic agents has the general formula ~ ~f~

~-C112J ~, ;

.

.,: . : . ..... , : . . . :

~C~37,3;~1~
where Rl and R2 are Cl to C4 alkyl and R~ 1~ a C10 to C24 alkyl group. An example of this group i8 the commerclal product "Quaternary" O of the Ciba-Geigy Corporation.
Another useful anti~tatic agent has the formula ~N~lR2R3X
where R i~ C12 to C22 alkyl; Rl-R2 CH3, CH2 2 CH2CH(CH~)OH; R~ is C~ , C2H5 or C6H5C ~ ; and X is Cl~ Br or CH3S04. An example is "Arquad" 18 sold by Armour Indu6trial Chemical Company. Still another useful compound is C12H250CH2-cH~o~-cH2-N(c~c ~ OH)2 CH~S04.
OH CH~

Satisfactory quaternary antistatlc agents can employ as anions halides, CH3S04, C2H5S04, ~ P04 and others.
The relative effectivenëss`of the antistatlc agents can be determined by preparing duplicate cleaning compositions distingulshed only by the difference in anti- -static agent employed, followed by application to a dark-colored textile article (preferably a test piece of nylon carpet) and removal by vacuuming9 each operation being performed in the same manner for each cleaning compositionO
Rubbing the toe end of the sole of a black shoe over the cleaned spot for about 10 strokes will cause the deposit of more or less polymer particles on the toe of the shoe depending on the efficiency of the antistatic agent.
As a result of the cationic antistatic component of the composltions, the particulate material does not adhere as tenaciously to the textile fibers as it would in the absence of the antistatlc agent. Essentially all of the particle~, eve~ those extxemely fine residual ~ragments which may h~ve been deposited due to break-up during the rubbing or brushing3 are readily removed by *Trade Marks 7 .

-~al37338 a vacuum cleaner or a brush. Where the antlstatic agent i~ not included, these small partlcles adhere to the textile fibers and, if in sufficien~ amount, conf'er an unde~lrable change in appearance, ~ "fro~ty" look9 to the - substrate O
As an antisettling agent a very fine insoluble inorganic material is employed~ exempllfied by ~umed silica which has a particle size o~ from about 0.01 to 0.007 micron. Such antisettling agent promotes the dispersion of the cleaning particulates ln the solvent and aids in providing a ~miform composition. A~ a~ additional anti-settling ald there can~ optionally, be included a small amount of ethylene gl~col or a polyethylene glycol of up to about 1,000 molecular weight.
The ~ollowing Examples illustrate the invention.
They do not limit the invention.
. .

Into a suitable vessel were charged 81.13 parts , s' of l,l,l-trichloroethane, with agitation~ There was 8UC- :
cesQively added 3.35 parts o~ 1,4-dioxane, 0.042 parts of secondary butyl alcohol, 0.042 par~s of 1,2-butylene oxide, o.626 parts of a 50~ aqueous ~olution of stearyltrimethyl-amm~nium chloride, and 0~511 parts o~ fumed silica o~
particle size 0.01 to 0~007 microns~ and the ingredlents were thoroughly mixed. There WaQ then added slcwly, allowing oach addition to wet out thoroughly~ 18~87 parts of urea-formaldehyde particulates having an 011 Value a~ove 90 and particle size b0tween 10 and 105 microns.
After thorough blending, the product was trans~erred to small containers for eventual use.

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Several n~lon carpeks that were badly solled were cleaned with the composit-Lon of thlq E:xample, in thi~
manner:
The cleaner was applied to the spots by shaking through a 1/32" opening in a bottle top to cover the area of the spots. The cleaner w~ ~ently worked ln with a nylon bristle brush. The applicatlon wa~ repeated a second time, and 30 minutes allowed ~or the solvent to evapora~e~ The residual particulate material was removed by a conventional beater type vacuum cleaner3 leaving no trace of the original spots~ Addition of 0.12 parts of ethylene glycol to the composition was found to help keep the particulate material suspended in the liquidO

A composition o~ the invention was prepared in the following manner for dispensing as an aerosol spray~
Into a vessel was placed 79.7 parts of inhibited methyl chloro~orm (95.9% l,l~l-trichloroethane, 4.0% 1,4-dioxane, 0.05~ 1~2-butyleneoxide and 0 25% 2-butanol) and ~.64 part o~ a 50% aqueous solution o~ stearyltrimeth~lammonium chloride~1002 part of fumed silica (particle size 0.01 to 0.007 micron) and 2Q.3 parts of urea-~ormaldehyde polymer particles were addedO A~ter thorou~h mixin~ the product was charged into a spray can cooled in a bath of rro~en carbon dioxide and 2504 parts of dichlorodifluoromethane was added.
The can was then ~itted with a spray head~ The polymer particles were prepared ln the same manner as described in Example 1. This composition was sprayed from the can on stained spots on carpets and chair upholstery and used as de~cribed in Exampl~ 1. Stained areas were cleaned so well that no trace o~ stain remained.

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A composition wa~ prepared as in Example 2 with the exception of certain proportions of materials that varled as follow~:
89.~ parts of inhiblted methyl chloroform, 0.~4 part of 50~ ~tearyltrimethyl~nonium chloride in i~o-propanol, 1.02 part of fumed ~ilica and 10.2 part3 of urea ~ormaldehyde polymer Particles with 25.~ part~ of dichloro~
difluorom~thane. This composition performed equally well when sprayed on textile stains and used as described in Ex~mple 1.

EXAMPLE 4 ~
By the g~neral procedure of Example 1, a pre- .
~erred cleaning composition can be made conta~nlng 10 part~ o~ urea-~ormaldehyde polymaric particles having a particle size between 10 and 105 mlcrons, 90 parts o~
1,131-trichloroethane, 1.0 part o~ stearyltrimethyl~mmoni~m ~ .
chloride catlonic antistatic agent9 and 1.0 part o~ ~umed ~ilica antisettling aæent.

~ 10 --'~ i .... . .. . . . . ...

Claims

CLAIMS:
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A liquid cleaning composition comprising i) 5 to 30 parts of urea-formaldehyde polymer particles having a particle size of from 10 to 105 microns and an oil value of at least 90 ii) 70 to 95 parts of halogenated solvent boiling at from 45° to 120°C., the total of i) and ii) being 100 parts, and iii) 0.1 to 3.0 parts of finely divided silica antisettling agent, iv) 0.1 to 2.0 parts of cationic antistatic agent, and v) up to 125 parts of aerosol propellant selected from at least one of trichloro-fluoromethane, dichlorodifluoromethane, 1,2-dichlorotetrafluoroethane, propane, isobutane and butane.

2. A composition according to Claim 1 comprising i) 10 to 23 parts of urea-formaldehyde polymer particles, ii) 77 to 90 parts of halogenated solvent, iii) 0.5 to 1 part of finely divided silica, iv) 0.3 to 1 part of cationic antistatic agent, and v) up to 50 parts or aerosol propellant.

3. A composition according to Claim 2 comprising i) 10 parts of urea-formaldehyde polymer particles, ii) 90 parts of 1,1,1-trichlorethane, iii) 1.0 part of fumed silica, and iv) 1.0 part of stearyl trimethylammonium chloride.